Control of pests with benzothienyl carbamates



United States Patent 3,288,673 CONTROL OF PESTS WITH BENZOTHIENYL CARBAMATES John R. Kilsheimer, Westfield, and Harold A. Kaufman, Piscataway Township, New Brunswick, NJ., assignors to Mobil Oil Corporation, a corporation of New York No Drawing. Filed Sept. 14, 1965, Ser. No. 487,333

Claims. (Cl. 167-33) This application is a continuation-impart of copending application Serial No. 427,089, filed January 21, 1965, which in turn is a continuation-in-part of copending application Serial No. 334,581, filed December 30, 1963, now abandoned, which in turn is a continuation-in-part of copending application Serial No. 220,073, filed August 28, 1962, now abandoned.

This invention relates to the production of new and useful chemical compounds. More particularly, it is concerned with the use of carbamates of benzothiophenes to combat pests.

It is a broad object of this invention to provide new chemical compounds. It is another object to prepare various carbamates of benzothiophenes. It is still another object to prepare compounds having insecticidal or other biological activity. A specific object is to provide pesticidal compositions containing such compounds. Another specific object is to provide a method for combating pests by contacting them with various carbamates of benzothiophenes. Other objects and advantages of this invention will become apparent to those skilled in the art, from the detailed description which follows:

The present invention provides N-alkyl, N-alkenylf and N-aryl carbamates of benzothiophenes having the formula:

where R is selected from H, alkyl (C -C cycloalkyl (C -C and alkenyl (C -C R is selected from H, alkyl (C -C alkenyl (C -C phenyl, and h'alophenyl; X, Y, and Z are selected from hydrogen, halogen, nitro, alkyl (C -C alkenyl (C -C di(C -C )a1kylamino, methylmerca-pto, cyano (CN), thiocyano (SCN), alkoxy (OCH to -OC H W is selected from O and S; 11:0, 1 or 2, i.e., n is '0-2; and in which the carbamate radical (OCW-NRR) and X, Y, and Z may be on any separate 2-7 positions of the ring; and the partially hydrogenated derivatives of said carbamates. 5

This invention also'provides a method of combating pests that comprises contacting them with carbarnates of benzothiop'hene having the formula described hereinbefore.

The following are typical compounds of this invention corresponding to the above generic formula:

" ice 3-isopropoxy-4-benzothienyl-N-methylcarbamate 7-isopropxy-4-benzothienyl-N-methylcarb amate 6-methyl-7-methoxy-4-benzothienyl-N-methylcarbamate 3-methyl-4-benzothienyl-N-methylcarbamate 7 -ethyl-4-benzothienyl-N-methylcarbamate 2ethyl-4-benzothienyl-N-methylcarbamate 7-methy1mercapto-4-benzothienyl-N-methylcarbamate 5-allyl-4-benzothienyl-N-methylcarbamate 7-nitro-4-benzothienyl-N-methylcarbamate 2-cyano-4-benzothienyl-N-methylcarbamate 7-cyano-4-benzothienyl-N-methylcarbamate 7-thiocyano-4-benzothienyl-N-methy1carbamate 2-chloro-4-benzothienyl-N-methylcarbarnate 3-chloro-4-benzothienyl-N-methylcarbamate 5-chloro-4-benzothienyl-N-methylcarbarnate 6-chloro-4-benzothienyl-Nmethylcarbamate 7-ehloro-4-benzothienyl-N-methylcarb amate 2,3-dichloro-4-benzothienyl-N methlcarbamate 2,3,5 ,6,7-pentachloro-4-benzothienyl-N-methylcarbamate 2-iodo-4-benzothienyl-N-methylcarbamate 3-bromo-4-benz-othienyl-N-methylcarbamate 3-benzothienyl-N-ethylcarbamate 4-benzothienyl-N-2-ethylhexylcarbamate 4-benzothienyl-N-n-butylcarbamate 4-benzothienyl-N-n-octylcarbamate 4-benzothienyl-N,N-dimethylcarbamate 4-benzothienyl-N-phenylcarbamate 4-benzothienyl-N-chlorophenylcarbamate 4-benzothienyl-N-phenylthionocarbamate 1, l-dioxy-4-benzothienyl-N-methylcarbamate 1 l-dioxy-3 -benzothienyl-N-methylcarb amate l-oxy-4 benzothienyl-N-methylcarbarnate 1-oxy-3-benzothienyl-N-methylcarbamate 4,5,6,7-tetrahydro-4-benzothienyl-N-methylcarbamate 2,3-dihydro-4-benzothienyl-N methylcarbamate 2,3-dihydro-7-rnethyl-4-benzothienyl-N-methylcarbamate 2,3-dihydro-7-methylmercapto-4-benzothienyl-N-methy1- earbamate 2,3-dihydro-5-chloro-4-benzothienyl-N-methylcarbamate The compounds of this invention can be made using various procedures. A convenient method generally applicable provides for the synthesis of a hydroxybenzothiophene as an intermediate and this compound is then converted to the N-alkyl or N,N-dialkyl carbamates, or the equivalent alkenyl or aryl carbamates, or carbamic acid.

Typically, 4-hydroxybenzothiophene is made according to the multistep synthesis of Fieser and Kennelly (Journal of the American Chemical Society, 57, page 1615, 1935).

The following examples, in which parts are by weight, illustrate these syntheses in detail:

EXAMPLE 1 The N-methylcarbamate derivative of the benzothiophene is made as follows: a reaction vessel equipped with a condenser and drying tube is charged with parts 4-hydroxybenzothiophene, 61 parts methyl isocyanate, 1 part dibutyltin diacetate, and 225 parts toluene. The solution is agitated at room temperature for 24 hours using a stirrer. The solution is then chilled and parts of solid product is obtained. This material has a melting point of 129 C. and analyzes as follows:

Theory Found Hydrogen, wt. percent 7. 4. Nitrogen, wt. percent 6.

Carbon, wt. percent The infrared spectrum of the product is also consistent with the structure 4-benzothienyl-N-methylcarbamate.

The reaction of this example can be illustrated as follows:

II OONHOH;

O H) S n A0) O H N C 0 methyl 492 2 isocyanate 4-hydroxy- 4-benzothienylbenzothiophene N-methylcarbamate Y EXAMPLE 2 The product of Example 1 can also be synthesized by the reaction of 4-hydroxybenzothiophene (A) with phosgene (B) in the presence of a 'base (e.g., alkali metal hydroxides or organic tertiary amines such as pyridine and triethyl amine) to give 4-benzothienyl chloroformate (C) and then the further reaction of this intermediate with methylamine (D) to yield the product 4-benzothienyl-N- methylcarbamate (E). This series of reactions is shown Other amines may be used in place of the methylamine (D) to give other corresponding carbarnates, e.g., cyclohexylamine, crotyl amine, allyl amine and the like.

The following is a more detailed description of the process of this example:

To an agitated mixture of 128 parts (1.3 M) of phosgene in 300 parts of toluene is added a solution of 150 parts (1.0 M) of 4-hydroxybenzothiophene and 127 .parts (1.05 M) of N,N-dimethylaniline in, 600 parts of toluene. The reaction mixture is then stirred at 30 C. for one hour. The mixture is cooled to 20 C. and added slowly to 600 parts of water maintained at 10 C. The excess phosgene is thus hydrolyzed and the N,N-di:methylaniline hydrochloride is removed in the aqueous phase. The oily layer is stripped of toluene at reduced pressure and the 4-benzothienyl chloroformate product is purified by distillation.

To a stirred solution of 212 parts (1.0 M) of the 4- benzothienyl chloroformate in 800 parts of toluene is added 310 parts of (2 M) of 20 percent aqueous monomethylamine. The reaction mixture is stirred at C. for thirty minutes to complete the reaction. The solid product is separated by filtration, washed thoroughly with water to remove all the methylamine hydrochloride, then washed with toluene and air dried. The 4-benzothienyl-N-methylcarbamate so obtained melts at 129 C. The yield is on the order of 90 percent.

EXAMPLE 3 The N,N-diall ylcarbamates can be made by the reaction of 4-benzothienyl chloroformate (C) (Example 2) with a .dialkylamine, such as dimethylamine in place of the methylamine (D) to yield the 4-benzothienyl-N, N-dimethylcarbamate. The reaction conditions are substantially the same as in Example 21 Nitrogen, wt. percent 4 EXAMPLE 4 Another method for preparing N-alkyl and N,N-dialkylcarbarnates is by the reaction of a hydroxybenzot'hiophene with the corresponding carbamyl halide. This is illustrated by the reaction of 4hydroxybenzothiophene and dimethylcarbamyl chloride in the presence of a tertiary organic amine (e.g., triethylamine) dissolved in benzene at a temperature of about C, for 3-4 hours to give a yield of 80-90% 4-benzothienyl-N,N-dimethylcarbamate. This carbamate has a B.P. of 165 C./ 1.4 mm. and analyzes as follows:

Theory Found Nitrogen, wt. percent OON tert. amine (CH )2NCC1 HCl s EXAMPLE 5 4-benzothienyl-N-ethylcarbamate Theory Found Nitrogen, wt. percent 6. 45 6. 38

EXAMPLE 6 4-benzothienyl-N-butylcarbamate In a similar manner as described in Example 5, are reacted 11 parts of n-butyl isocyanate and 15 parts of 4- hydroxybenzothiophene. A white solid, M.P. 78-81 C. is obtained. Analysis:

Theory Found EXAMPLE 7 4-benz0thienyl-N-phenylcarbamate In a similar manner as described in Example 5 are reacted 13.1 parts of phenyl isocyanate and 15 parts of EXAMPLE 8 4-benzozhienyl-N- (m chlorophenyl) carbamate In a similar manner as described in Example 5 are reacted 15 parts of 4-hydroxybenzothiophene and 16.9 parts of m-chlorophenyl isocyanate. A white solid (7.5 parts), M.P. -117 C. is obtained. Analysis:

Theory Found N itr'ogeii; at. percent 4. 55

EXAMPLE 9 4-benz0thienyl-N-(p-chlorophenyl) carbamate In a similar manner as described in Example 5 are reacted 16.9 parts of p-chlorophenyl isocyanate and parts of 4-hydroxybenzothiophene. A white solid (18.9 parts), M.P. 165166.5 C., is obtained. Analysis:

I Theory Found Nitrogen, wt. percent 1 EXAMPLE 1O 3 -benzoth ienyl-N -methy lcarbamate Theory Found Nitrogen, wt. percent 6. 73

EXAMPLE 1 1 5 -benzothicny l-N -methylcarbamate Theory Found Nitrogen, wt. percent 6. 76 l EXAMPLE 12 6-benz0thienyl-N-m ethylcarbamate In a similar manner as described in Example 5 are reacted 8 parts of 6-hydroxybenzothiophene and 3.5 parts ture, 4-benzothienyl-N-methylcarbamate-1,l-dioxide. Recrystallized material, M.P. 158159 C. (benzene, methanol) analyzes as follows:

I Theory Found Carbon, wt. percent 50. 2 50.0; 49. 9 Hydrogen, wt. percent 3. 8 3. 9; 3. 8 Nitrogen, wt. percent 5. 9 5. 9

The reaction of this example can be illustrated as follows:

EXAMPLE 15 4-benzothienyl-N-cyclopropylcarbamate A cooled reaction vessel is charged with 11.5 parts phosgene and 52 parts toluene followed 'by a solution of 12.5 parts 4-hydroxybenzothiophene and 10.5 parts dimethylaniline in 48 parts toluene while keeping the temperature below 20 C. After stirring one hour at 20 C. the mixture is transferred to a reaction vessel previously charged with 50 parts ice water. The mixture is stirred 45 minutes at 10 C. and 30 minutes at room temperature. The top, organic layer is removed, dried over Drierite, and concentrated to 24 parts of a solution of 4-benzothienyl chloroformate in toluene. Vapor phase analysis indicates product of greater than 95% purity.

The toluene solution of 4-benzothieny1 chloroformate is charged With 45 parts toluene to a chilled reaction vessel. Cyclopropy-l amine, 9.5 parts, in 8.5 parts toluene is charged over a period of 20 minutes with cooling to control the exotherm. After stirring at 10 C. for 20 minutes, the crystalline materials are filtered and triturated with water to remove cyclopropylamine hydrochloride. Dried product, 7 parts, has melting point 97-99 C. Concentration of the filtrate gives an additional 4.8 parts product, M.P. 9497. The product analyzes as of methyl isocyanate, using benzene as the solvent. A 45 follo s; white solid (5.4 parts), M.P. 128.5 C., is obtained. Analysls: I Theory 1 Found Theory Found Carbon 61.7 61. 7; 61. 7 o Hydrogen 4.8 5.1; 5.2 Nitrogen 6. 0 6.2; 5. 9 Nitrogen, wt. percent 76 75 Sulfur 13. 7 14.1; 13. 7

EXAMPLE 13 The infrared spectrum of the product is consistent with 7-benz0thienyl-N-methylcarbamate In a similar manner as described in Example 5 are reacted 3.6 parts of 7-hydroxybenzothiophene and 1.6 parts of methyl isocyanate using benzene as the solvent. A white solid (3.3 parts), M.P. 139 C., is obtained. Analysis:

Theory l Found Nitrogen, wt. percent 6. 76 I EXAMPLE 14 4-benzothienyl-N -methylcarbamate-'1 ,1 -dz'oxide An open vessel is charged with 15 parts 4-benzothienyl- N-methylcarbamate, 105 parts acetic acid and 41 parts 30% hydrogen peroxide. After 84 hours the solution is poured into 350 .parts ice water. Upon further cooling 13 parts of product are collected, M.P. 143-156 C. Infrared and ultraviolet spectra are consistent with the structoluene as the solvent. A white solid (11.5 parts), M.P. 88-89 C., is obtained. Analysis:

Theory Found Carbon, wt. percent 56. 8 57. 1 Hydrogen, wt. percent 6. 2 6. 6 Nitrogen, wt. percent 6. 6 6.8

EXAMPLE 17 7-methyl-4-b enzothienyl-N-methylcarbamate In a similar manner as described, in Example 5 are reacted 2 parts of 4-hydroxy-7-methylbenzothiophene and 7 0.8 part of methyl isocyanate, using toluene as the solvent. A white solid (2 parts), M.P. 141.5142 C., is obtained. Analysis:

Theory Found Carbon, wt. percent 59. 7 59. 5 Hydrogen, wt. percent 5.0 6. 6 Nitrogen, wt. percent 6. 3 6. 2

EXAMPLE 18 7-methylmercapto-4-benzothieny l-N-methylcarbamate In a similar manner as described in Example 5 are reacted 2.2 parts of 4-hydroxy-7-methylmercaptobenzothiophene and 0.7 part of methyl isocyanate, using toluene as the solvent. White solid platelets (2.1 parts), M.P. 121.5-122, are obtained. Analysis:

Theory Found Carbon, wt. percent 52. 2 52. 2 Hydrogen, wt. percent 4. 3 4. 5 Nitrogen, wt. percent 5. 5 5. 5

EXAMPLE 19 5-chlor0-4-benz0thienyl-N-methylcarbamate In a similar method as described in Example 5 are reacted 4.8 parts of 4-hydroxy-5-chlorobenzothi-ophene and 1.6 parts of methyl isocyanate, using toluene as the 4 -benzth ienyl-N -pr0pargylcarbwmate In a similar manner as described in Example 2 are reacted 9.7 parts of 4-benzothienyl chloroformate and parts of propargylamine, using toluene as the solvent. A white solid (1.5 parts), M.P. 9395 C., is obtained. Analysis:

Theory Found Carbon, wt. percent 62. 3 62. 4 Hydrogen, wt. percent 3. 9 3. 9 Nitrogen, wt. percent 6. 1 6. 0

EXAMPLE 21 2,3 -dihydro-4-benz0thienyl-N -methylcarbamate- 1,1-di0xide A solution of 15 parts of 4-benzothienyl-N-methylcarbamate-1,1-dioxide in methyl alcohol is reduced by hydrogen (50 p.s.i.g.) at 25 C. for 1.5 hours, using 10% palladium on charcoal, as catalyst. A White solid (14 parts), M.P. 132.5134.5 C., is obtained. Infrared and ultraviolet analyses correspond to the desired 2,3-dihydro 4 benzothienyl-N-methylcarbamate-l,l-dioxide. Analysis:

Theory Found Carbon, wt. percent 49. 8 Hydrogen, wt. percent 4. 6

In general, when using the isocyanate processes of Examples 1, 5-13 and 1619 or the carbamyl chloride process of Example 4, it is better to use a slight molar excess of 210 percent of the isocyanate or carbamyl chloride as compared to the hydroxybenzothiophene in order to insure complete reaction. The reaction temperature is not too critical and can vary from below room temperature, up to 100 C. or higher. However, a reaction temperature of 25 C. to C. has been found to be very satisfactory under most conditions. The reaction can be run below or above atmospheric pressure but a pressure of about 1 atmosphere or slightly above has been found to be very satisfactory. Any inert solvent, such as benzene, toluene, diethyl ether, etc. can be used as the solvent for the isocyanate or carbamyl chloride reaction with the hydroxy intermediates. Tin compounds, such as dibutyltin diacetate and tertiary amines, such as triethylamine or pyridine can be used as catalysts, but the reaction will also proceed in their absence, albeit somewhat more slowly. Likewise, the conditions set forth for the reactions of the examples are not limited to the exact proportions, temperatures, pressures, etc. given therein.

The alkenyl and aryl carbamate compounds are prepared in the same manner as set forth for the alkyl compounds, using the equivalent alkenyl or aryl compounds in place of the alkyl compounds set forth as reactants. Thus, compare Examples 7, 8, 9, and 20 with Example 5. Also, the thiocarbamates of this invention having a -OCSNRR' radical can be formed in the same manner shown above by using the equivalent thio compounds, i.e. by using thioisocyanates, thiophosgene, thiochloroformates or thiocarbamyl halides. These thio compounds have a sulfur atom attached to a carbon atom instead of the oxygen atom in the isocyanates, phosgene, chloroformates or carbamyl halides used to prepare carbamates of this invention having the OCONRR' radical. This invention also includes the partially hydrogenated carbamates,

such as the 2,3-dihydrobenzothienyl-carbamates or -thioapplied as dusts, as liquid sprays, or as gas-propelled sprays and can contain, in addition to a carrier, additives such as emulsifying agents, wetting agents, binding agents,

gases compressed to the liquid state, odorants, stabilizers and the like. A wide variety of liquid and solid carriers can be used in the pesticidal compositions. Non-limiting examples of liquid carriers include Water; organic solvents such as alcohols, ketones, amides, and esters; mineral oils such as kerosene, light oils, and medium oils; and vegetable oils such as cottonseed oil. Non-limiting examples of solid carriers include talc, bentonite, diatomaceous earth, pryophyllite, fullers earth, gypsum, flours derived from cotton seeds and nut shells, and various natural and synthetic clays having a pH not exceeding about 9.5.

. The amount of the compounds of this invention utilized in pesticidal compositions will vary rather widely. It depends to someextent upon the type of composition in which the material is being used, the nature of the condition to be controlled, and the method of application (i.e., spraying, dusting, etc.). In the ultimate pesticidal composition, as applied in the field, carbamate pesticide concentrations as low as 0.0001 weight percent of the total composition can be used. In general, compositions, as applied, containing about 0.05 weight percent pesticide in either liquid or solid carrier give excellent results. In some cases, however, stronger dosages up to about 10 weight percent may be required.

In practice, pesticidal compositions are usually prepared in the form of concentrates, which are diluted in the field to the concentration desired for application. For example, the concentrate can be a wettable powder containing large amounts of the compound of this invention, a carrier (e.g. attapulgite or other clay), and wetting and dispersing agents. Such powders can be diluted prior to application, by dispersing it in water to obtain a sprayable suspension containing the concentration of pesticide desired for application. Other concentrates can be solutions that can be later diluted, e.g. with kerosene. Thus, it is within the contemplation of this invention to provide pesticidal compositions containing up to about 80 percent, by weight of the composition, of a pesticidal compound of this invention. Accordingly, depending upon whether it is ready for application or it is in concentrated form, the contemplated pesticidal compositions contain between about 0.0001 percent and about 80 percent, by weight of the composition, of a pesticidal compound of this invention and a carrier, liquid or solid, as defined hereinbefore.

The following examples illustrate typical pesticidal compositions of several types. Parts are by weight.

EXAMPLE 22 A wettable powder concentrate, that is diluted to desired concentration by dispersing it in Water, has the following composition:

Parts 4-benzothienyl-N-methylcarbamate 50 Attapulgite 47 Mono-calcium salt of polymeric alkylaryl sulfonic acid (Daxad 21dispersant) 2 Sodium alkylnaphthalene sulfonate (Nekal BA- 75Wetting agent) 1 EXAMPLE 23 A liquid concentrate that is diluted in the field with kerosene has the following composition:

Parts 4-benzothienyl-N-methylcarbamate 37.6

n-Propanol 231.7

Cottonseed oil 32.9

Dimethyl formamide 65.8

EXAMPLE 24 A liquid formulation that is suitable for spray application contains:

Parts 4-benzothienyl-N-methylcarbamate 1 Acetone 20 Kerosene 79 EXAMPLE 25 Three granular formulations for application against soil insects were prepared. In each case. 53.6 parts 4-benzothienyl-N-methylcarbamate was dissolved in 303 parts acetone to form a spray solution. In one formulation, spray solution was sprayed onto 906 parts montmorillonite clay (20-40 mesh) and then the solvent was evaporated off. In a second formulation, spray solution was sprayed onto 906 parts corn cob granules and solvent evaporated off. In a third formulation spray solution was sprayed onto 906 parts ground pecan shells and solvent evaporated off.

The following results are typical of the high biological activity of the compounds of this invention as used, for instance, against the Lepidoptera and Coleoptera classes, such as the southern armyworm (Prodenia eridania Cram), and Mexican bean beetle (Epilachna varivestis Muls.), etc., and as measured by the LD value (concentration required to kill 50% of the test insects). In these tests the compounds are formulated as wettable powders and then diluted in water to the concentrations of actual chemical indicated. Reference Standards, such as DDT, etc., are formulated in a similar manner:

Cranberry bean plants are dipped in the appropriate concentrations of the respective formulations and then allowed to dry. Third instar larvae are then caged on the treated plants and maintained under greenhouse conditions for 48 hours following which mortality counts are made. Three replicates are used for each level of application and then the LD is calculated from the dosage mortality figures. The observed data for the compound of this invention and DDT are shown in tabular form below:

LD u in Parts per Million Compound Mexican Southern Bean B eetle Armyworm 4-b en zothienyl-N-rnethylcarbamate 2. 5 40 D D '1 100 100 The insecticidal activity of a series of these compounds can be demonstrated by the following data:

The 4-benzothienyl-N-methylcarbamate shows activity not only as an insecticide but also as a fungicide, such as for the protectant control of leaf rust of wheat. Cheyenne wheat plants approximately 7 days old are sprayed just short of run-01f with an acetone-water mixture containing a wetting agent and 1000 parts per million on a weight basis of 4-benzothienyl-N-methylcarbamate. Tthe plants are allowed to dry and then are inoculated with the parasite Puccinia rubigo-vera. After the chemically treated and untreated plants have been inoculated in a similar fashion they are placed in a moist chamber with a relative humidity of greater than 95 percent. After 16 hours the plants are removed from the moist chamber and placed on the greenhouse bench. The degree of infection is determined approximately 6-7 days later by counting the number of infection loci per plant. Using 1000 p.p.m. of 4-benzothienyl-N-methylcarbamate as -a protectant solution, the percent control of the organism Puccinia rubigo-vera was percent. The untreated plants had an average of 151 infection loci per plant.

In general, it has been found that the other compounds of this invention exhibit biological activity and utility. Thus, 4-benzothienyl-N-ethylcarbamate (Example 5) at 1000 p.p.m. gave 82% protection against leaf rust of wheat. 4-benzothienyl-N-butylcanbamate (Example 6) exhibited 47% activity against leaf rust of Wheat when tested at 1000 p.p.m. Against the house fly, 4-benzothienyl-N-phenylcarbamate (Example 7) gave 7% control.

In the following tabulation is set forth the percent kill of Mexican bean beetle effected by various other com pounds of this invention, when each was tested at a concentration of 1000 p.p.m.:

. 12 Typical test results with pesticides contemplated herein are set forth in the following table:

Percent Kill at Root Knot 2-Spotted Compound 1,000 p.p.m. Compound Nematode, Spider Mite, Mexican Bean Control Mortality Beetle 4-benzothienyl-N-methyloarbamate 100 8 4-benzothienyl-N-methylcarbamate-l,l-dioxide- 53 3-benzothienyl-Nmethylcarbamate 100 6 4-benzothienyl-Ncyclopropylcarbarnate 100 5-benzothienyl-N-methylcarbamate 100 14 4,5,6,7-tetrahydro-4-benzothienyl-N-methylcarba- 7-benzothienyl-N-methylcarbamate 93 20 mate 7 10 4-1)enzothienyl-N-bntylcarbamate 73 5 7-methyl-4-benzothienyl-N-methylcarbamate *100 (8) 4-benzothienyl-N,N-dimethylcarba- 7-methyl-4-benzothienyl-N-methylcarbamate *100 (0. 7) mate 76 7 5-chloro-4-benzotheinyl-N-methylcarbamate- *100 (8) 7-methyl4-benzothienyl-N-methyl- 4-benzothienyl-N-propargylcarbamate 100 carbamate *100 (50) 2,3-dihydro-4-benzothienyl-N-methylcarbamate- 7-methy1-4-benzothien l N-methyl- 1,1-dioxide 100 oa-rbamatm *100 (900) Other insecticidal activity of typical pesticides contem- Although the present invention has been described with plated herein is set forth in the following tabulation as preferred embodiments, it is to be understood that modifipercent kill, when tested at a concentration of 1000 cations and variations may be resorted to, without dep.p.m. The values in parentheses are the LD parting from the spirit and scope of this invention, as

Compound Armyworm Pea Aphid House Fly 4-benzothienyl-N-methylcarbamate. 100 68 49 (75) (750) 3-benzothienyl-N-rnethylcarbamate 0 15 0 4-benzothienyl-N,N-dimethylcarbamate 0 lgg) 7 4-benzothieny1-N-(o-chlorophenyl) carbamate 0 17 0 7-methyl-4-benzothienyl-N-methylcarbamate 100 77 54 (10) 7-methyl-4-benzothienyl-N-methylcarbamate 27 ($88) 0 5-chloro-4-benzothienyl-N-methylcarbamate 33 56 0 7-benzothienyl-N-methylcarbamate 40 90 51 Other types of pesticidal activity contemplated within those skilled in the art will readily understand. Such the scope of this invention are nematocidal and miticidal variations and modifications are considered to 'be within activity. Test procedures used are as follows: the purview and scope of the appended claims.

NEMATOCIDE What is Claimed is: Candidate Compounds at a rate of 100 ppm. (mm-W 1 The process of combating pests Whl'Cl'l comprises con- 5 tasting them with one of the carbamates of benzothioalent to 200 lbs. per acre) are umformly mixed with soil henes havin the followin formula containing eggs and knots of the root-knot organism, p g g Meloidogyne incognita. Single-eye seed pieces of presprouted Kennebec potatoes, grown in sand, are then transplanted to the treated soil, the best age for such transplant being about eight to ten days. When significant evidence of nematode development is detectable in the untreated controls, -by soil surface knots and/or knots on the root system itself, treated plants are than observed for comparative root knot development. Percentage root 55 knot control is computed based on the ratio of knot present on the treated plants to knots present on the un- $3 53 i g g izg 22 2 fi a z g treated controls. An initial count of knots at the soil f g 1 8 selece d 5 surface is made. Plants with few or no knots are then i g s i g 6 g Washed free of soil and a count of the total number of 1 (C C i 6 y g a knots present within the root system is made. g y 1 4 a my 2- 1( kylamino, methylmercapto, cyano CN), thiocyano MITICIDE SCN), and alkoxy (OCH to OC H W is se- Candidate compounds are formulated as wettable lected from O and "S; n is an integer from 0 to 2; and in powder concentrates by adding to an inert carrier conwhich the carbamate radical (OCWNRR') and X, Y, taining 2 weight percent wetting agent, and grinding to a and Z may be on any separate 2-7 positions of the ring; uniform blend on a ball mill. Respective formulations and the partially hydrogenated derivatives of said carbaare then diluted in water to concentrations of actual mates. chemical indicated. p 2. The process of claim 1 in which said carbamate of Cranberry bean plants infested with various life stages 7 benzothiophene is 4-benzothienyl-N-methylcarbamate. of the two-spotted spider mite are dipped in appropriate 3. The process of claim 1 in which said carbamate of concentrations of the respective formulations and allowed benzothiophene is S-benzothienyl-N-methylcarbamate. to-dry. Treated plants are maintained under greenhouse 4. The process of claim 1 in which said carbamate of conditions for 72 hours and then observed for percentage benzothiophene is 7-benzothienyl-N-methylcarbamate. mortality and plant injury. Three replicates are used 7 5. The process of claim 1 in which said carbamate of for each level of application. I 75 benz-othiophene is 4-benzothienyl-N,N-dirnethylcarbamate.

6. The process of claim 1 in which said carbamate of benzothiophene is methyl-4-benzothienyl-N-methylcarbamate.

7. The process of claim 6 in which said carbamate of benzothiophene is 7-methyl-4-benzothienyl-N-methylcarbamate.

8. The process of claim 1 in which said carbamate of benzothiophene is methylmercapto 4 benzothienyl N- methylcarbamate.

9. The process of claim 8 in which said carbamate of benzothiophene is 7 methylmer'capto 4 benzothienyl- N-methylcarbamate.

19. A pesticidal composition comprising a carrier, for a pesticide and between about 0.0001 percent and about 80 percent, by weight of said composition of one of the carbamates of benzothiophenes having the following generic formula:

where R is selected from H, alkyl (C -C cycloalkyl (C C and alkenyl (C -C R is selected from H,

methylmercapto, cyano (-CN), thiocyano (SCN), and alkoxy OCH to --OCBH17); W is selected from O and S; n is 0-2; and in which the carbamate radical (-OCWNRR) and X, Y, and Z may be on any separate 2-7 positions of the ring; and the partially hydrogenated derivatives of carrier is a mixture of acetone and kerosene.

References Cited by the Examiner UNITED STATES PATENTS 2,786,851 3/1957 Mahan 260-330.5 3,000,781 9/ 1961 Feichtinger et al 167-33 3,008,872. 11/1961 Goodhue et a1 167-33 3,070,606 12/1962 Anderson 260330.5

LEWIS GOTTS, Primary Examiner.

R. HUFF, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,288,673 November 29, 1966 John R. Kilsheimer et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3, lines 3 to 11, for that portion of the formula reading:

(CH) Sn(OAc) read (C H J Sn(OAC] line 60, strike out "of", first occurrence; column 4, line 31 for "in diacetate" read tin diacetate column 5 line 74, for "l43-l56 C." read l53l56 C. column 11,

first table, second column, lines 4, 5 and 6 thereof, and column 12, first table, third column, lines 7 and 8 thereof, the asterisk should appear to the right of the numbers shown in parentheses, each occurrence; column 14, line 2,

for "-OCH to OC H read (-OCH to OC H Signed and sealed this 12th day of September 1967.

(SEAL) Attest:

ERNEST W. SWIDER Attesting Officer EDWARD J. BRENNER Commissioner of Patents 

1. THE PROCESS OF COMBATING PESTS WHICH COMPRISES CONTACTING THEM WITH ONE OF THE CARBAMATES OF BENZOTHIOPHENES HAVING THE FOLLOWING FORMULA: 1-(O=)N,(R-N(-R'')-C(=W)-O-),X,Y,Z-1-BENZOTHIOPHENE WHERE R IS SELECTED FROM H, ALKYL (C1-C8), CYCLOALKYL (C3-C6), AND ALKENYL (C2-C8); R'' IS SELECTED FROM H, ALKYL (C1-C8), ALKENYL (C2-C8), PHENYL, AND CHLOROPHENYL; X, Y, AND Z ARE SELECTED FROM HYDROGEN, HALOGEN, NITRO, ALKYL (C1-C4), ALKENYL (C2-C4), DI(C1-C2)ALKYLAMINO, METHYLMERCAPTO, CYANO (-CN), THIOCYANO (-SCN), AND ALKOXY (-OCH3 TO -OC8H17); W IS SELECTED FROM O AND S; N IS AN INTEGER FROM 0 TO 2; AND IN WHICH THE CARBAMATE RADICAL (-OCWNRR'') AND X, Y, AND Z MAY BE ON ANY SEPARATE 2-7 POSITIONS OF THE RING; AND THE PARTIALLY HYDROGENATED DERIVATIVES OF SAID CARBAMATES. 